Dyeings on cellulose esters



Patented Nova 29,1938 i 2,138,553

UNITED STATES PATENT OFFICE DYEINGS ON CELLULOSE ESTERS Friedrich Wilhelm Muth, Leverkusen I. G.- Werk, Germany, assignor to General Aniline Works, Inc., New York, N. Y., a corporation of Delaware No Drawing. Application July 7, 1936, Serial No. 89,470. In Germany July 1'], 1935 11 Claims. (Cl. 8-50) The present invention relates to a process for of the present invention, there may be menthe manufacture of azo dyestuffs on cellulose tioned by way of example 1-, 2-, or 3-hydroxydiesters, especially cellulose acetate silk, and to the phenyleneoxide, 3,6-dihydroxydiphenyleneoxide, dyed cellulose esters obtained thereby, more par- 3-hydroxydiphenyleneoxide-2-carboxylic acid, 3-

5 ticularly it relates to a process for the manufachydroxydiphenylene-sulfide 2 carboxylic acid,

ture on cellulose esters, especially cellulose acetate 3,6-dihydroxydiphenyleneoxide 2,7 dicarboxylic silk, of dyestufis, which may be represented by acid, 3,6-dihydroxydiphenylenesulfide-2,'7-dicar-- the general formula: boxylic acid, 2 hydroxyphenanthrene 3 carl I boxylic acid, 3 hydroxyphenanthrene 2 carlo OH boxylic acid, 1, 2-, 3-, or4-hydroxyphenanthrene,

'dihydroxyphenanthrene, Z-hydroxyfiuorene, 4- N=N R hydroxyfluorene, 2-hydroxyfiuorene-3-carboxylic acid, Z-hydroxyfluorenone, 3-hydroxyfiuoreone 3 3 d gg gfig fi gg ig g g gg 2-carboxylic acid and similarly constituted acids. s02, s-S, CH2, co, CH=CH, R stands for the Example 1 radical of a diazotization component, which, it 1% f i nis ppl e to acetate artificial being self-understood, may b ar n azo o n silk in the usual manner, diazotized on the fiber stands for one of the numbers 1 and 2, wherein a d e ped f half an u W 0f the hydroxy group stand in ortho-position t hydroxyphenanthrene dissolved with caustic the azo group, and wherein the benzene nuclei o y fi s a Ordinary temperature and t e may bear carboxylic acid groups as substituents. at a p r tu e w i h i r ly r i to 6 The new dyeings onthe cellulose esters, especial- C. Then the dye 1S seeped in the usual m ly cellulose acetate silk, are obtained by applying n A e p e h brown of good faStneSS D D- to the cellulose acetate silk, an aromatic base or ertieS is b e amino azo compound, diazotizing and coupling in The dyestufi COTIeSIJOIIdS t0 the follOWing a neutral, weakly alkaline or acid bath with a 1111119;

coupling component of the general formula: OH

| H OCH: OCH: H? H Ht wherein X and 12 means the same as stated above O and wherein the benzene nuclei may bear car- 35 boxylic acid groups as substituents.

The method of producing developing azo dye- Example 2 stuffs on cellulose esters, especially cellulose 0.8% of the dyestuff paminobenzene-azo-aacetate silk, has been described, e. g. in German naphthylamine isdyed in the usual manner on Patents 446,220 and 549,641. By the new process acetate artificial silk, diazotized on the fiber and 40 there are obtained, depending on the specific developed for half an hour with 3% of 3-hydroxycomponents used, various shades, especially dark phenanthrene dissolved with caustic soda lye, as brown to blackish brown shades, which in every described in Example 1, and then the dyeing is respect are of good fastness properties and which soaped. A dark brown dyeing of good fastness are distinguished by an improved dischargeability, properties is obtained. 7

and in part by an improved fastness to light. The dyestufi corresponds to the following for- As coupling components, suitable for the process mula: 0H 0H 50 I G1 w MQ H? (6H Hi3 CH Amino azo-toluene The dyestuff corresponds to the following formula:

COOH O In an analogous manner are obtained:

By combination ol-- I claim: I

1. A process which comprises applying to a cellulose ester a diazotization component suitable for the manufacture of azo dyestuiIs, diazotizlng and coupling with a compound of the group consisting of diphenylene compounds of the general formula:

wherein X stands for a member selected from the group consisting of O, S, $0, $02, S-S, CH2, CO, CH=CH and 1!. stands for one of the numbers l and 2, and such derivatives thereof, bearing in the benzene nuclei a carboxyllc acid group.

2. A process which comprises applying to a cellulose ester a diazotization component suitable p-Agiuobenzene-azo-a-naphthylamine Aminoazo-benzene..

B-hydrox 'diphenylene-oxide-Z-mrboxylic acid. 3 hgtiroxydiphenylenesulfide 2- carboxylic 3-hydroxyphenanthrene 3-hydroxydiphenylenepxide" do 34mgroxydiphenylene-oxide-ilmrboxylic acid. o

A brown. A yellowish brown.

A brown,

A yellowish brown.

A reddish brown.

A deep reddish brown. A yellowish brown.

, A reddish dark brown.

A brown.

A rust brown.

A blackish brown.

A reddish brown. Oran Olive-brown.

Khaki Age coupling: grayish m-Amido benzoic acid +o-anisidiue ..d0 a g dish brown. 2 rhloro 4 nitraniline dimethylaniline (reduced) "do A reddish brown. 3,3-dimethoxy4,4-diaminodiphenyL. do Abvioletish blackish rown.

Do 3,6*dihydroxyphenanthreue A dark brown. p-Amido benzenH-naphthylamine d0 l i 3,3'-dimethoxy-4,4'-diaminodiphenyL 3-hydroxydiphenylene-sulfide-2-mrboxylic b lo et s dark aci rown. 3-hydroxyphenanthrene-2-carboxylic acid- 'Z-hydroxyfluorene A reddish brown. 2-hydroxydiphenylene-oxide DO- Neutral coupling: A Amino arc-benzene 3,( dihydroxydiphenylaneoxidm g f gfifik A dun reddish orange. Neutral coupling: A Amido axe-toluene ..do ggz fif gfifia reddish brown.

Neutral coupling: A rn-Amido benzoic acid-l-o-anisidine. do "f,'g

garnet. Neutral muplmg: A 2-chlor0-i-nitramliue-dimethylaniline (redo mlensh brown.

duced). Acid coupling: A dull garnet. Neutral coupling? A p-Amido benzene-a-napbthylamine "do g g gg gggg i vim tish brown. Neutral coupling: A u-Naphthylamine ..do gggj f fgg w letish brown. Neutral coupling: A 3.3'-dimethoxy-l,4'-djalninodiphenyl ..do gfg gig gg i vb letish brown. Neutral coupling: A Aminodiazobenzene 3.6-dihydroxydiphenylenesulfide g ;g$ A rem dish brown.

Neutral coupling: A 2-chloro-4-nitraniline dlmethylaniline (redo violetish brown.

ducedl. Acid coupling: A (or inth brown. Neutral coupling: A p-Amido benzenea-naphthylamine... do g g g:&?' A

' brown.

Neutral coupling: A 3,3-dimethory-4,4'-dieminodiphenyl do .i ggm ggii I ish brown.

for the manufacture of azo dyestuffs, diazotizing and coupling with a diphenylene compound of the general formula:

wherein X stands for a member selected from the group consisting of O, S, SO, S02, SS, CH2,

CO, CH=CH and n stands for one of the numbers 1 and 2, and such derivatives thereof, bearing in the benzene nuclei a carboxylic acid group.

5. Cellulose esters dyed with dyestufis of the general formula:

wherein X stands for a member selected from the group consisting of O, S, SO, S02, S-S, CH2, CO,

) CH=CH, R stands for the radical of a diazotization compound and n stands for one of the numbers 1 and 2, and wherein the hydroxy group stands in o-position to the azo group and such derivatives thereof bearing in the benzene nuclei a carboxylic acid group.

6. Cellulose esters dyed with the dyestuff of the following formula:

7. Cellulose acetate silk dyed with'dyestuffs of the general formula:

tic/U wherein X stands for a member selected from the group consisting of O, S, SO, S02, S-S, CH2, CO, CH CH, R stands for the radical of a diazotization compound and n stands for one of the numbers 1 and 2, and wherein the hydroxy group stands in o-position to the azo group and such derivatives thereof bearing in the benzene nuclei a carboxylic' acid group.

8. A process which comprises applying to a cellulose ester a diazotization component suitable for the manufacture of azo dyestuffs, diazotizing and coupling with a 3,6-di-hydroXy-diphenylene oxide.

9. A process which comprises applying to a cellulose ester a diazotization component suitable for the manufacture of azo dyestuffs, diazotizing and coupling with a 3,6-di-hydroxy-diphenylene sulfide.

10. A process which comprises applying aminoazo-benzene to a cellulose ester, diazotizing and coupling with a 3,6-di-hydroxy-di-phenylene oxide.

11. A process which comprises applying aminoazo-benzene to a cellulose ester, diazotizing and coupling with a 3,6-dihydroxy-diphenylene sulfide.

FRIEDRICH WHJHELM MUTI-I. 

